Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
  • C10G47/16—Crystalline alumino-silicate carriers
  • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/068—Noble metals

Definitions

• process for hydrocracking hydrocarbons which comprises contacting such hydrocarbons with said catalyst in the presence of a hydrogen-containing gas at a pressure fro-m normal to 200 leg/cm. and a temperature from 150 C. to 600 C.
• This invention relates to a method of preparing hydrocracking catalysts having very high activity and a process for hydrcracking hydrocarbons using such catalysts to produce lower-boiling hydrocarbons.
• hydrocracking catalysts which comprises utilizing crystalline aluminosilicates of the zeolite type having openings from about to 15 A. in their largest dimension as a support for at least one metal of the platinum group or a compound of such metal in the proportion '"from about 0.01 to 20% by weight based on the metal and then halogenating the resulting aluminosilicate composition with one or more halogenated hydrocarbons containing fluorine and/or chlorine at a temperature from 0 C. to 400 C. to ahalogen content from about 0.05 to 15% by weight based on the substrate, and
• Catalysts heretofore used for the hydrocracking generally comprised composite containing one moiety capa- ;ing function include acidic oxides such as, for example, silica-alumina, boria, silica titania zirconia, silica alumina-magnesia,
• silica-magnesia silica-zirconia, silicaalumina-boria, boron fluoride-alumina and the like. These catalysts have not proved to be completely satisfactory.
• compositions containing at least one metal of the platinum group or a compound thereof supported on crystalline aluminosilicates of the zeolite type have been considered superior in hydrocracking activity and selectivity compared to such prior catalysts as silica-alumina and the like.
• crystalline aluminosilicate of the zeolite type alone as the component for cracking.
• halogens have been introduced from aqueous solutions of HCl, HF, NH F or the like. Suitable processes are described, for example, in Japanese Patent Publication 12,319/ 1963 which utilizes alumina plus Cl ion, Japanese Patent Publication 22,261/ 1963 which utilizes silica-magnesia plus F ion, and Japanese Patent Publication 318/ 196-8 which utilizes silica-alumina plus F- ion.
• halogenated hydrocarbons including CHClF CCl F and CO1
• crystalline aluminosilicates of zeolite type supporting a metal of the platinum group such as platinum or palladium or a compound thereof capable of performing hydrogenation function, under selected conditions to intro Jerusalem halogens into the latter.
• the catalytic compositions thus obtained are characterized by their outstanding catalytic activities in hydrocracking of hydrocarbons.
• hydrocracking catalysts are prepared by a method which comprises bringing crystalline aluminosilicates of zeolite type with openings from 5 to 15 A. and supporting at least one metal of the platinum group or a compound thereof into contact with selected halogenated hydrocarbons containing fluorine and/or chlorine to produce catalysts having a halogen content from about 0.05 to 15% by weight based on the substrate.
• Typical useful divalent or higher metal ions include Mg, Ca, Sr, Ba, Zn, Cd, Mn, Ni, Co, Cu, Al, rare earth metals and the like.
• the ratio of the exchange is at least about 50%, and in preferred catalysts it is at least 80%. The ratio may be measured by absorption spectrophotometry and represents a ratio of the number of sodium atoms replaced with hydrogen or polyvalent metal atoms to the number of sodium atoms originally present.
• Metals of the platinum group such as platinum, palladium, rhodium or iridium or compounds thereof are placed on the substrate by the conventional procedures, such as impregnation or ion exchange.
• the compounds may be oxidation, reduction or sulfidation products.
• the amount of the metal or compound additive is preferably about 0.01 to 20% by weight in terms of the metal on the basis of the crystalline aluminosilicate of zeolite type.
• a bonding agent such as bentonite may be incorporated if desired before utilizing such molding procedures as extrusion or tabletting. Products containing less than 0.01% by weight are generally unsatisfactory, whereas those containing more than about 20% by weight are not economical.
• halogenated hydrocarbons used in this invention are hydrocarbon compounds in which one or more of the hydrogens are substituted with chlorine and/or fluorine.
• useful compounds include CH CI CHCl CCl CH F CHF CF CH CIF, CHClF CHCI F, CClFg, CCl F, CCl FCClF C H F and the like.
• Halogenation is preferably effected in the vapor phase. For that reason compounds containing from one to about six carbon atoms are preferred since they are most readily vaporized.
• a crystalline aluminosilicate of the zeolite type which supports a metal or a compound thereof capable of performing hydrogenating function is thoroughly dried under such as gas as hydrogen, nitrogen, oxygen or air at 350- 550 C. for two hours or longer and, while maintaining a predetermined temperature, contacted with at least one of the halogenated hydrocarbon mentioned above, preferably in association with a non-reducing gas such as nitrogen, oxygen or air for a predetermined period of time and then with the non-reducing gas alone in order to expel the unreacted materials.
• the product is cooled and stored under moisture-proof conditions.
• the reaction may be conducted either in a flowing reaction tube or in a closed vessel.
• the halogen content can be adjusted by control of the reaction temperature and the amount of halogenating agent employed.
• the halogen content is adjusted to about 0.05 to 15% by weight since there is little advantage in increasing the halogen content above this level.
• the selected halogenation temperature is an important feature of this invention. Generally at increased temperatures more halogen is introduced in a given-period of time. However too high a temperature will result in destruction of the crystalline aluminosilicate to produce products with little or no activity. Moreover, certain of the metals orcompounds thereof-capable of i performing the hydrogenating function may react with the'halogenating agent to forin low boiling compounds which are lost by p 4 volatilization. Therefore, the halogenation temperature is preferably as low as is consistent with'obt'aining reaction. Normally this is in the range from about 0 to 400 C., preferably from 100 to 300 C.
• the optimum method of control will depend upon the halogen content desired and the nature of the halogenating agent, since the halogenating agents individually differ in reactivity with crystalline aluminosilicate; Certain 'of them are reactive at relatively low temperatures at which others have little tendency to react. In practice; it is preferred to use the most active halogenating, 'a'g e nts.
• the preferred halogenating agents are CH Cl CHClg, CCl CHClF CCl F CClF --CClF C H F.
• the hydrocracking reaction of hydrocarbons by the use of the catalyst preferred according to the invention is carried out under the following conditions.
• the reaction temperature may vary from about 15-0to 600 C., preferably from 200 to'550 C.;
• the reaction pressure is from about normal to 200 kg./cm. preferably from normal to 150 kg./cm.
• the space velocity is from about 0.50 to 20.0 wt./wt./hr., preferably from 0.1 to 10.0 wt./wt;/ hr.;
• the volume ratio of hydrogen to hydrocarbon is preferably from 100 to 4,000 l./l.
• the hydrocarbons used-in the invention include ordinary hydrocarbons, particularly petroleum hydrocarbons such as naphtha, kerosene, light oil or vacuum distillation-distillate oil.
• the catalysts of this invention manifest improved activity in hydrocracking, superior resistance to organic nitrogen and reduced formation of coke.
• Table 1 indicates that halogenated catalysts B and C are superior in cracking activity to non-halogenated catalyst A.
• EXAMPLE 3 In 1.5 liters of 10% aqueous solution of NH NO were placed 200 g. of commercially available zeolite molecular sieve of NaY type and the mixture was heated with stirring at 90 C. for about 2 hours for the ion exchange. The procedures were repeated nine times followed by another exchange using 1.5 liters of 10% aqueous solution of Mg(NO to exchange 88% of the original sodium with NH and Mg++. Then, the resulting mass was transferred into an aqueous solution containing ions to bring the carrier to carrying palladium as much as about 0.5% by weight. The catalyst was washed with water and, following addition of bonding agent as much as about 20% by weight, molded, dried at 120 C. and calcinated at 500 C. The resulting catalyst is referred to as Catalyst E.
• Catalyst F In a quartz reaction tube were placed 10 g. of Catalyst E, and the catalyst was dried and reduced under hydrogen at 500 C. for 3 hours and then cooled to 200 C. CHClF was passed over the catalyst maintained at 200 C. at a flow rate of 50 ml./rnin. together with nitrogen gas at a flow rate of 100 mL/min. for 10 minutes. Nitrogen gas was passed for about 1 hour after the reaction and the resulting catalyst was stored in a moisture-proof vessel. Chlorine and fluorine in the catalyst were aanlyzed to be 0.60% by weight and 0.44% by weight, respectively. The product is referred to as Catalyst F.
• Table 2 indicates that halogenated catalyst F exerts a higher activity than with non-halogenated catalyst E.
• reaction conditions were adjusted in such a manner that a ratio of decomposition of 20-30% was obtained with either catalyst.
• the reaction conditions and properties of the products are shown in Table 3.
• a process for hydrocracking hydrocarbons which comprises contacting a starting hydrocarbon with a catalyst in the presence of a hydrogen-containing gas at a pressure from about normal to 200 kg./cm. and a temperature from about 150 C. to 600 C., said catalyst being produced prior to contacting the starting hydrocarbon by halogenating a substrate comprising a crystalline aluminosilicate of zeolite type with openings from 5 to 15 A. in their largest dimension and supporting a metal of the platinum group or a compound thereof in the proportion from about 0.01 to 20% by Weight in terms of the metal with at least one halogenated hydrocarbon in which the halogen is selected from the group consisting of fiuotime and chlorine, at a temperature of from about 0 to about 400 C. to a halogen content from about 0.05 to 15% by Weight on the basis of the substrate.
• aluminosilicate is a sodium aluminosilicate which contains equimolar quantities of A1 0 and Na O. r i
• a process as in Claim 3 is at least References Cited UNITED STATES PCATENTS wherein the exchange ratio 3,316,169 4/1967 Peek at al. 208111 3,318,802 5/1967 Martin 208111 3,440,300 4/1969 Estes et al. 252-441 3,551,516 12/1970 Ashley et al. 25244l 3,691,255 9/1972 Takase et al. 252455 Z 3,699,056 10/1972 Takase et al.

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• Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Cited By (4)

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• 1970
  • 1970-11-14 JP JP45099809A patent/JPS5027044B1/ja active Pending
• 1971
  • 1971-11-10 US US00197365A patent/US3835026A/en not_active Expired - Lifetime
  • 1971-11-12 DE DE2156324A patent/DE2156324C3/de not_active Expired
  • 1971-11-12 FR FR7140630A patent/FR2113961B1/fr not_active Expired
  • 1971-11-12 GB GB5277971A patent/GB1376333A/en not_active Expired

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